JP2002055226A - Polarizing element and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polarizing element having the improved adhesibility at a low cost and additionally enabling to manufacture a large area polarizing element and a method for manufacture the same. SOLUTION: A substrate film 12 containing at least a kind of compound selected from a group of compounds A and/or B for a substrate film raw material as a main component is formed on a reference surface 11a of a glass substrate 11. A metal dispersion film 13 is formed on the substrate film 12 by coating it with a coating liquid containing at least a kind of compound of an element selected from a metal compound and a group of raw materials of a metal dispersion film coating liquid as a main component. Subsequently fine metal particles 14 with anisotropy in shape are selectively deposited on a film boundary surface 16 between the substrate film 12 and the metal dispersion film 13 by heat or electromagnetic wave irradiation treatment. Thereby the adhesibility and wear resistance of the substrate film 12 and the metal dispersion film 13 are improved and at the same time, the large area polarizing element becomes manufacturable at a low cost.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to optical communication, optical recording,
The present invention relates to a polarizing element used for an optical sensor and the like and a method for manufacturing the same. More specifically, the present invention relates to a polarizing element in which metal fine particles are selectively deposited on a film interface between a base film and a metal dispersion film on a transparent substrate, and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, a plurality of metal layers and dielectric layers are alternately laminated on a substrate such as glass by using a thin film forming process such as vacuum deposition or sputtering, and then, at a temperature higher than the softening point of the substrate. 2. Description of the Related Art There is known a polarizing element in which polarization characteristics are developed by stretching a substrate and deforming a metal layer into a discontinuous island-like metal particle layer oriented in the stretching direction, and a method of manufacturing the same.

Further, there is known a multi-layer laminated type polarizing element in which a dielectric thin film and a metal thin film are alternately laminated over several hundred layers by using the above-mentioned thin film forming process to exhibit polarization characteristics.

[0004]

However, in a polarizing element in which polarization characteristics are developed by heating and stretching an alternately laminated film composed of the metal layer and the dielectric layer, the substrate is elongated to form a metal particle layer. Therefore, there is a problem that deformation and surface roughness are generated on the surface of the alternately laminated film after the heat stretching, thereby deteriorating the polarization characteristics and increasing the loss due to scattering and the like. Also,
In a multilayer laminated polarizing element in which a dielectric thin film and a metal thin film are alternately laminated, a problem that peeling between the multilayer films easily occurs due to poor adhesion between the metal thin film and the dielectric thin film. there were. Furthermore, when producing a multilayer laminated polarizer, it is necessary to form a metal layer on a substrate such as glass using a thin film forming process such as vacuum evaporation or sputtering, which is not suitable for cost reduction. was there.

[0005] In addition, the polarizing elements that are put into practical use using the prior art have a small area, and there is a problem that the applications are limited. The present invention has been made in view of the above problems, and its object is to improve adhesion at low cost,
In addition, another object of the present invention is to provide a polarizing element capable of manufacturing a polarizing element having a large area and a manufacturing method thereof.

[0006]

In order to solve the above-mentioned problems, the invention according to claim 1 is to form a base film containing a component having an action of attracting metal fine particles on a transparent substrate. After forming a metal dispersion film by applying a coating solution containing metal ions on the base film, selectively depositing metal fine particles at a film interface between the base film and the metal dispersion film. .

[0007] According to a second aspect of the present invention, on a transparent substrate,
Titanium oxide, cerium oxide, tin oxide, bismuth oxide,
Cobalt oxide, copper oxide, aluminum oxide, magnesium oxide, manganese oxide, chromium oxide, indium oxide,
Group consisting of vanadium oxide, iron oxide, nickel oxide, zinc oxide, tungsten oxide, tantalum oxide, hafnium oxide, barium oxide, ytterbium oxide, niobium oxide, molybdenum oxide, yttrium oxide, ruthenium oxide, germanium oxide, lead oxide, and boron oxide (Hereinafter, this group is referred to as “base film raw material compound group A”). A base film containing at least one compound selected from the group consisting of a metal compound, silicon, zirconium, and titanium is formed on the base film. , Cerium, tin, bismuth, cobalt,
Copper, aluminum, magnesium, manganese, chromium,
A group consisting of indium, vanadium, iron, nickel, zinc, tungsten, tantalum, hafnium, barium, ytterbium, niobium, molybdenum, yttrium, ruthenium, germanium, lead, and boron. A) a coating liquid containing at least one compound selected from the group consisting of a base material and a metal dispersion film by applying a heat treatment or an electromagnetic wave irradiation to form a metal dispersion film. Metal fine particles are selectively deposited at the film interface with the above.

According to a third aspect of the present invention, in the method of manufacturing a polarizing element according to the first or second aspect, the base film is a group consisting of silicon oxide and zirconium oxide (hereinafter, this group is referred to as a base film). (Hereinafter referred to as “raw material compound group B”).

According to a fourth aspect of the present invention, in the method for manufacturing a polarizing element according to any one of the first to third aspects, the base film raw material compound group A is represented by mass%. At least one compound selected from the group consisting of
It is characterized by containing 100% by mass and 0 to 98% by mass or less of at least one compound selected from the base film raw material compound group B.

According to a fifth aspect of the present invention, in the method for manufacturing a polarizing element according to any one of the first to fourth aspects, the coating liquid as a raw material of the metal dispersion film becomes a solid. 0.2% to 50% by mass of a metal, silicon oxide, zirconium oxide, titanium oxide, cerium oxide, tin oxide, bismuth oxide, cobalt oxide, copper oxide, aluminum oxide, magnesium oxide, manganese oxide; Chromium oxide, indium oxide, vanadium oxide, iron oxide, nickel oxide, zinc oxide, tungsten oxide, tantalum oxide, hafnium oxide, barium oxide, ytterbium oxide, niobium oxide, molybdenum oxide, yttrium oxide, ruthenium oxide, germanium oxide, lead oxide ,
It is characterized by containing 50 to 99.8% by mass of at least one compound selected from the group consisting of boron oxide (hereinafter, this group is referred to as a metal dispersion film raw material compound group).

According to a sixth aspect of the present invention, there is provided a polarizing element manufactured by the method according to any one of the first to fifth aspects. <Operation> In the polarizing element and the method of manufacturing the same according to the present invention,
The phenomenon that metal fine particles are deposited at the film interface between the underlayer film and the metal dispersion film is explained by a sol-gel method for producing a glass plate coated with a colored film. That is, when a colored film-coated glass plate in which fine gold particles are dispersed in a silica film serving as a matrix is obtained by the sol-gel method, for example, J. Am. Sol
-Gel. Sci. Techn. 1,305-312
In (1994), since the growth process of the gold fine particles and the contraction process of the matrix occur simultaneously in the drying process of the sol, there is a phenomenon that the network structure of the silica matrix is rapidly contracted, and the gold fine particles are repelled out of the film. That is, in the present invention, for example, paying attention to the deposition behavior of metal fine particles in the curing process of a sol containing a metal compound such as this phenomenon, at the film interface between the base film and the metal dispersion film,
It is intended to precipitate metal fine particles.

Further, at the film interface between the underlayer film and the metal dispersion film,
The reason that the metal fine particles are selectively deposited is that the metal in the metal dispersion film is attracted by the interaction between the metal in the metal dispersion film and the underlying film (for example, electrostatic action), and the sol is cured. It is presumed that the metal fine particles gather at the film interface before the formation. Therefore, in the present invention, by combining such a phenomenon and the precipitation behavior of metal fine particles in the curing process of the sol containing the metal compound described in the sol-gel method described above, the film of the base film and the metal dispersion film is formed. This is a unique phenomenon in which metal fine particles are selectively segregated at the interface.

Hereinafter, the composition of the underlayer will be described. The substance contained in the base film raw material compound group A has a function of attracting metal fine particles when the coating solution containing the metal compound is subjected to heat treatment or electromagnetic wave irradiation and is reduced, and the base film and the metal dispersion film It has the effect of increasing the adhesion of Therefore, by adjusting the composition ratio of one or more compounds selected from this group, it is possible to control the behavior of the metal fine particles to precipitate at the interface of the base film, specifically, to control the particle diameter of the precipitated metal fine particles. it can.

Among the substances contained in this group, titanium oxide, cerium oxide, tin oxide and bismuth oxide have a large effect of attracting metal fine particles and are suitably used. The content of the substance contained in the base film raw material compound group A is determined by, when the base film is baked, titanium oxide (TiO ₂ ),
Cerium oxide (CeO ₂ ), tin oxide (SnO ₂ ), bismuth oxide (Bi ₂ O ₃ ), cobalt oxide (CoO), copper oxide (CuO), aluminum oxide (Al ₂ O ₃ ), magnesium oxide (MgO), Manganese oxide (MnO ₂ ), chromium oxide (Cr ₂ O ₃ ), indium oxide (In ₂ O ₃ ),
Vanadium oxide (V ₂ O ₅ ), iron oxide (Fe ₂ O ₃ ), nickel oxide (NiO), zinc oxide (ZnO), tungsten oxide (WO ₂ ), tantalum oxide (Ta ₂ O ₃ ), hafnium oxide (HfO) ₂ ), barium oxide (BaO), ytterbium oxide (Yb ₂ O ₃ ), niobium oxide (Nb
O ₂ ), molybdenum oxide (MoO ₂ ), yttrium oxide (Y ₂ O ₃ ), ruthenium oxide (RuO ₂ ), germanium oxide (GeO ₂ ), lead oxide (PbO), and boron oxide (B ₂ O ₃ ) 2 to 100% by mass, and more preferably 5 to 100% by mass. When the content is less than 2%, the effect of attracting the fine metal particles is not exhibited, and the fine metal particles do not precipitate at the film interface between the base film and the metal dispersion film.

Further, other compounds that interact with the metal in the metal dispersion film, for example, the substances contained in the base film raw material compound group B are opposite to the function of the base film raw material compound group A to attract metal fine particles. Therefore, it can be applied as a component for controlling the behavior of the metal fine particles to be deposited at the interface of the underlayer, specifically, the particle diameter of the deposited metal fine particles. These substances are appropriately mixed and used with the base film raw material compound group A according to the purpose.

The content of the base film raw material compound group B is determined based on the values of silicon oxide (SiO ₂ ) and
Expressed in mass% in terms of zirconium oxide (ZrO _2), it is preferably 0 to 98 wt%, more preferably 0-9
5% by mass. When the content exceeds 98%, metal fine particles do not precipitate at the interface of the underlayer.

In addition to the above-mentioned metal oxides, an organic compound having an action of coordinating with a metal may also have a behavior in which metal fine particles are deposited at the interface of the underlayer, specifically, the particle diameter of the deposited metal fine particles. It can be applied as a component of a base film to be controlled. The organic compound includes an amino group, SS
Organic compounds having a functional group such as a group or an SH group are preferably used.

Next, the composition of a coating solution containing as a main component a metal compound and a compound of at least one element selected from the group of coating materials for a metal dispersion film will be described.
The metal compound is an important material that is reduced by heat treatment or electromagnetic wave irradiation, and is precipitated as metal fine particles from the metal dispersion film at the interface of the base film to impart polarization characteristics. Therefore, by adjusting the content of the metal, the polarization characteristics of the obtained polarizing element can be controlled.

As the metal, a noble metal is preferably used, and more preferably, gold or silver is used. The content of the metal fine particles is preferably from 0.2 to 50% by mass, more preferably from 0.5 to 20% by mass in terms of% by mass. If the content as the metal fine particles exceeds 50% by mass, the amount of the metal fine particles segregating at the film interface between the base film and the metal dispersion film increases, and the adhesion between the base film and the metal dispersion film decreases. If it is less than 0.2% by mass, effective polarization characteristics cannot be obtained.

Preferably, the heat treatment is performed at a temperature of 200 ° C. or higher. When performing electromagnetic wave irradiation, it is preferable to use ultraviolet rays having high energy. Among the metal dispersion film raw material compounds, silicon oxide and zirconium oxide are preferably used because the sol as a coating solution can be easily adjusted and the characteristics described below can be used.

When the fine metal particles segregate at the film interface between the base film and the metal dispersion film, the silicon oxide binds to the base film,
The effect of improving the adhesion between the base film and the metal dispersion film is shown. Further, it also has a role of assisting the segregation of the metal fine particles to the film interface between the base film and the metal dispersion film. In particular, in the case of gold, as described above, since the growth process of the gold fine particles and the contraction process of the matrix occur simultaneously in the drying process of the sol, the network structure of the silica matrix is rapidly contracted, and the gold fine particles are ejected out of the film. Show action.

Zirconium oxide, like silicon oxide,
It has an effect of improving the adhesion between the base film and the metal dispersion film by binding to the base film. Further, it has a role of assisting segregation of the metal fine particles to the film interface between the base film and the metal dispersion film, and also has a role as a refractive index adjuster.
Therefore, when it is necessary to match the refractive index with the base film as an optical element, the refractive index can be controlled by adjusting the content of zirconium oxide.

The content of the raw material compound of the metal dispersion film is represented by 5% by mass when the coating solution is baked to form an oxide, taking into account the content of the metal fine particles exhibiting polarization characteristics.
0-99.8 mass% is preferable.

[0024]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, as shown in FIGS.
a, a base film 12 containing, as a main component, at least one compound selected from a base film raw material compound group A and / or B, and a metal compound and a metal dispersion film coating liquid raw material are formed on the base film 12. After forming a metal dispersion film 13 by applying a coating solution containing a compound of at least one element selected from the group as a main component, the base film 12 and the metal dispersion film are heated or irradiated with electromagnetic waves. 13
The metal fine particles 14 having shape anisotropy are selectively deposited at the film interface 16 with the film. In addition, having the shape anisotropy,
It has an aspect ratio greater than 1.

Next, raw materials for forming the base film and the metal dispersion film will be specifically described below. In particular, among the methods for forming a film, raw materials in the case of employing a coating method such as a thermal decomposition method using a solution as a starting material, a roll coating method, and a spin coating method will be described.

First, raw materials of titanium oxide, cerium oxide, tin oxide and bismuth oxide which are preferably used among the compounds included in the base film raw material compound group will be described. As a raw material of titanium oxide, titanium organic compounds such as titanium alkoxide, titanium acetylacetonate, and titanium carboxylate are preferably used. As the titanium alkoxide, generally, titanium (OR) ₄ (R is 4 carbon atoms)
From the viewpoint of reactivity, titanium isopropoxide and titanium butoxide are preferred. It has also been known that in the case of titanium, the use of a β-diketone complex chelated with acetylacetonate or the like is preferable from the viewpoint of stability. In this case, as a general formula, titanium (OR) _m L _n (m + n
= 4, n ≠ 0), where L is acetylacetone. In this case, β such as acetylacetonate
-Chelation with a diketone complex or the like may be used, or commercially available titanium acetylacetonate may be used. Furthermore, use of an organic acid salt such as acetic acid, propionic acid, and acrylate can be considered.

Alternatively, fine titanium oxide particles may be used.
For example, photocatalytic titanium oxide fine particles (trade name “STS-01” (particle size (X-ray particle size) 7 nm) manufactured by Ishihara Sangyo Co., Ltd.),
“STS-02” (particle size (X-ray particle size) 7 nm), “CS
-N "), titania sol" M-6 "manufactured by Taki Kagaku Co., Ltd.
(ST-K01) and “ST-K03” manufactured by Ishihara Sangyo Co., Ltd. in addition to commercially available aqueous dispersion sols such as (crystallite size 5 nm).
And a commercially available water-alcohol mixed solvent-dispersed titania sol containing a binder.

As a raw material of cerium oxide, cerium organic compounds such as cerium alkoxide, cerium acetylacetonate, and cerium carboxylate can be suitably used. In addition, cerium inorganic compounds such as nitrates, sulfates and chlorides can also be used, but cerium nitrate and cerium acetylacetonate are preferred from the viewpoint of stability and availability.

The raw material of tin oxide is SnCl_Four(C_nH
_{2n + 1}) (Where n = 1 to 4), C _FourH₉SnCl_Three,
(CH_Three)_TwoSnCl_Two, (C_FourH₉)_TwoSn (OCOC
H_Three), Such as organotin and tin tetrabutoxide
Organic tin alkoxides and the like can be used.

As a raw material of bismuth oxide, bismuth nitrate, bismuth sulfate, bismuth chloride and the like, a complex obtained by chelating bismuth with a β-diketone such as acetylacetone, and bismuth (III) t-pentoxide are preferable.

The silicon oxide and zirconium oxide raw materials that are particularly preferably used among the compounds included in the metal dispersion film raw material compound group will be described. As a raw material of silicon oxide, metal alkoxide is preferable, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
Tetrabutoxysilane and the like can be mentioned. A condensate (n ≧ 2) or a mixture of the condensates is also conveniently used. Specific examples of the condensate include hexaethoxydisiloxane (n = 2), octaethoxytrisiloxane (n = 3), decaethoxytetrasiloxane (n = 4), and ethoxypolysiloxane (n ≧ 5). Can be used. Ethyl silicate 40 consisting of a mixture of a monomer (n = 1) and a condensate (n ≧ 2) [composition: C
ihlar, Colloids and Sur
faces A: Physicochem. Eng. A
specs 70 (1993) p. 253-268.
And the monomer (n = 1) by mass fraction: 1
2.8% by mass, dimer (n = 2): 10.2% by mass, 3
Monomer (n = 3): 12.0% by mass, tetramer (n = 4):
7.0 mass%, multimer (n ≧ 5): 56.2 mass%, ethanol: 1.8 mass%]. Further, an alkyl trialkoxysilane in which the alkoxy group of the above compound is substituted with an alkyl group can also be used. For example, an alkoxy group is a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group, a linear or branched alkyl group such as an octyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, Alkenyl groups such as vinyl group, allyl group, γ-methacryloxypropyl group, γ-acryloxypropyl group, phenyl group, toluyl group, aryl group such as xylyl group, benzyl, aralkyl group such as phenethyl group or γ- Examples thereof include those substituted with a mercaptopropyl group, a γ-chloropropyl group, a γ-aminopropyl group, and the like.

As raw materials for zirconium oxide, tetramethoxyzirconium, tetraethoxyzirconium,
Tetraisopropoxy zirconium, tetra n-propoxy zirconium, tetraisopropoxy zirconium isopropanol complex, tetraisobutoxy zirconium, tetra n-butoxy zirconium, tetra sec-
Butoxyzirconium, tetra-t-butoxyzirconium and the like can be conveniently used. Further, zirconium alkoxide obtained by chelating the above zirconium alkoxide with a β-ketoester compound is also preferably used. Examples of chelating agents include methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, and butyl acetoacetate.
CH ₃ COCH ₃ COOR, where R is CH ₃ , C
₂ H ₅ , C ₃ H ₇ , or C ₄ H ₉ ) can be listed, among which acetoacetate alkyl esters, especially methyl acetoacetate and ethyl acetoacetate, It is preferable because it can be obtained at a reasonable cost. The degree of chelation of the zirconium alkoxide may be part or all, but it is preferable to chelate at a molar ratio of (β-ketoester) / (zirconium alkoxide) = 2 because the chelate compound is stable. Chelating agents other than the β-ketoester compound, for example, zirconium alkoxides chelated with acetylacetone are insoluble in solvents such as alcohols, and thus precipitate, making it impossible to prepare a coating solution. Furthermore, it is also possible to use alkoxyzirconium organic acid salts in which at least one of the alkoxy groups of the above zirconium alkoxide is replaced with an organic acid such as acetic acid, propionic acid, butanoic acid, acrylic acid, methacrylic acid, and stearic acid. .

The method for forming the underlayer 12 is not particularly limited. For example, a film can be directly formed on the glass substrate 11 using a thin film forming process such as vacuum evaporation or sputtering. When using a thermal decomposition method, a spin coating method, a roll coating method, or the like, the base film material is dissolved in an organic solvent to prepare a base film coating solution, and after applying this on a transparent substrate, By a method of heating at a temperature of 200 ° C. to 800 ° C. for 5 to 200 minutes to form a film,
It is preferably formed on the glass substrate 11.

The metal dispersion film 13 is formed by dissolving the metal dispersion film raw material in an organic solvent, applying a coating solution onto the base film, and then heating the coating solution at a temperature of 200 ° C. to 800 ° C. for 5 to 200 minutes. Irradiation with ultraviolet light of 1 to 400 nm at 1 μw or more for 0.01 second to 30 minutes is formed on the base film 12.

The method for applying the coating solution is not particularly limited, but examples thereof include a casting method, a dip coating method, a gravure coating method, a flexographic printing method, a roll coating method, a spray method, and a spin coating method. Used for

The organic solvent used for the coating solution depends on the method for forming each film. For example, as an organic solvent used in a casting method or a dip coating method, a solvent having a high evaporation rate is preferable. When a solvent having a low evaporation rate is used, drying of the coating film is delayed, so that the flowability of the applied coating liquid is increased and a uniform coating film may not be formed. Suitable organic solvents used in the casting method and the dip coating method include, for example, alcohol solvents having a high evaporation rate such as methanol, ethanol, isopropyl alcohol, and tert-butoxy alcohol. on the other hand,
As the organic solvent used in the gravure coating method, flexographic printing method, roll coating method and the like, a solvent having a low evaporation rate is preferable. When a solvent having a high evaporation rate is used, the solvent evaporates before sufficient leveling is not performed, so that the appearance of the applied coating may become dirty. Here, the evaporation rate of the solvent is generally evaluated by a relative evaporation rate index with butyl acetate being 100. Solvents with this value below 40 are classified as solvents with very slow evaporation rates. Suitable organic solvents used in the gravure coating method, flexographic printing method and roll coating method include, for example, ethyl cellosolve, butyl cellosolve, cellosolve acetate, diethylene glycol monoethyl ether, hexylene glycol, diethylene glycol, ethylene glycol, tripropylene glycol, dipropylene glycol, and the like. Examples include acetone alcohol and tetrahydrofurfuryl alcohol. The solvent of the coating liquid desirably contains at least one of such solvents, but a plurality of the above solvents may be used depending on the coating method, characteristics of the coating liquid, segregation behavior of the metal fine particles, and the like.

The polarizing element according to the present invention is a metal element 1
Due to the segregation phenomenon of No. 4, light of a specific polarization plane is selectively absorbed, and polarization characteristics are exhibited. Here, the metal fine particles 14
As shown in FIG. 1,, isotropically precipitates at the interface of the base film 12 in a direction parallel to the base film 12, so that the polarization characteristics of the polarizing element of the present invention exhibit direction dependency.

Hereinafter, embodiments of the present invention will be described. (First Embodiment) As shown in FIG. 3, a polarizing element according to the present embodiment is provided on a reference surface 11a substantially perpendicular to the incident direction of light on the glass base material 11 and substantially perpendicularly to the reference surface 11a. A plurality of plate-like base films 12 containing as a main component at least one compound selected from base film raw material compound groups A and / or B are formed so as to project at intervals. The method of forming the pattern structure of the base film 12 is not particularly limited. For example, exposure techniques such as flexo patterning, photolithography, and the like, a lift-off technique, an electron beam drawing technique, A drawing technique, a laser two-beam interference exposure technique, a laser abrasion, a pattern transfer by a press, and the like are preferably used. In this embodiment, the underlying film has a line width of 0.1 to 2.0 μm.
m, line spacing 0.1-2.0 μm, depth 0.1-20 μm
Is formed. And
A metal dispersion film 13 containing, as a main component, a metal compound and at least one compound selected from a metal dispersion film raw material compound group is formed between the plurality of plate-like base films 12;
At the film interface 16 between the base film 12 and the metal dispersion film 13, metal fine particles 14 are deposited and formed.

Therefore, the polarizing element in this embodiment is
As shown in FIG. 3, for light from a direction perpendicular to the reference plane 11a, it exhibits a polarization characteristic of absorbing an S-polarized component and transmitting a P-polarized component.

As described above, since the metal fine particles 14 are isotropically deposited on the interface of the base film 12 in the direction parallel to the base film 12, various patterns of the pattern structure of the base film 12 can be changed. A polarizing element having polarization characteristics can be manufactured. For example, the uneven structure when viewed from the substrate surface as shown in FIG.
It can be selected according to the application and required characteristics such as oval and diamond.

(Second Embodiment) As shown in FIG. 4, a polarizing element according to this embodiment has a base film material compound group A on a reference surface 11a of a glass substrate 11 which is inclined with respect to the light incident direction. And / or at least one selected from B
Film 12 containing a metal compound and at least one compound selected from a metal dispersion film raw material compound group as a main component
3 are stacked as a set, and a plurality of
Metal fine particles 14 are deposited and formed at a film interface 16 between the metal and the metal dispersion film 13.

Therefore, the polarizing element according to this embodiment exhibits a polarization characteristic of absorbing an S-polarized component and transmitting and reflecting a P-polarized component with respect to light from a direction inclined with respect to the reference plane 11a.

(Third Embodiment) As shown in FIG. 5, a polarizing element according to this embodiment includes a base film material compound group A and / or B selected from a group consisting of base film material compounds A and / or B on a reference surface 11a of a glass substrate 11. A set of a base film 12 containing one compound as a main component and a metal dispersion film 13 containing a metal compound and at least one compound selected from a metal dispersion film raw material compound group as a main component. The metal particles 14 are deposited and formed at the film interface 16 between the base film 12 and the metal dispersion film 13.

The polarizing element according to this embodiment exhibits a polarization characteristic of absorbing an S-polarized component and transmitting a P-polarized component for light from a direction parallel to the substrate surface.

(Fourth Embodiment) As shown in FIG. 6, a polarizing element according to this embodiment has at least a base film material compound group A and / or B selected on a reference surface 11a of a glass substrate 11. A base film 12 containing one compound as a main component, a metal dispersion film 13 containing a metal compound and at least one compound selected from a metal dispersion film raw material compound group as a main component are laminated, The metal fine particles 1 are formed on the film interface 16 between the base film 12 and the metal dispersion film 13.
4 is formed by precipitation. In addition, on the outer surfaces of the glass substrate 11 and the metal dispersion film 13, a reflection enhancing film 15 for repeatedly reflecting incident light inside the polarizing element is provided.

The polarizing element in this embodiment absorbs the S-polarized component with respect to the light that is obliquely incident on the reference plane 11a from one end of the element and is repeatedly reflected inside the element. It shows a polarization characteristic of transmitting a polarization component. Therefore, according to the polarizing element of this embodiment, only the P-polarized light component of the incident light can be extracted, and the light can be repeatedly reflected on the inner surface of each of the reflection enhancing films 15 and guided to a desired location. Hereinafter, technical ideas grasped from the above embodiments will be described below. (1) A method for manufacturing a polarizing element, comprising forming a metal-containing metal dispersion film on a transparent substrate, and then selectively depositing metal fine particles from the metal dispersion film on the surface of the metal dispersion film.

Focusing on the precipitation behavior of the metal fine particles during the curing process of the sol in the sol-gel method, it is possible to produce a large-area polarizing element by selectively depositing the metal fine particles from the metal dispersion film on the surface layer of the metal dispersion film. It becomes possible.

(2) forming a base film on the transparent substrate,
The method according to (1), wherein after forming the metal dispersion film on the base film, the metal fine particles are selectively deposited on a film interface between the base film and the metal dispersion film. Production method. A base film is formed on a transparent substrate, a metal dispersion film is formed on the base film, and then fine metal particles are selectively deposited on a film interface between the base film and the metal dispersion film, whereby the base film and the metal dispersion film are dispersed. It is possible to manufacture a polarizing element with improved adhesion to a film. (3) The method for producing a polarizing element according to the above (2), wherein the base film contains a compound exhibiting an interaction with the metal fine particles. When the base film contains a compound that interacts with the metal fine particles, the deposition behavior of the metal fine particles, specifically, the particle diameter of the precipitated metal fine particles can be controlled. (4) The method according to any one of (1) to (3), wherein the metal fine particles are selectively deposited on the surface of the metal dispersion film from the metal dispersion film by performing heat treatment or electromagnetic wave irradiation. The method for producing the polarizing element according to the above. By performing the heat treatment or the electromagnetic wave irradiation, the metal fine particles can be easily precipitated from the metal dispersion film on the surface layer of the metal dispersion film.

[0049]

EXAMPLES Hereinafter, the above embodiments will be described more specifically with reference to examples, but the present invention is not limited by these examples. (Examples 1 to 3) Using a glass substrate as a substrate, 10c
A titanium oxide base film and a segregated gold (Au) -containing silicon oxide film are formed on a glass substrate of mx 10 cm. A glass substrate is placed in a sputtering apparatus, and a target having a purity of 9
A 9.99% titanium oxide target was used. In the sputtering, a titanium oxide film having a thickness of 1 μm was formed at a deposition rate of 40 nm / min. A line and space pattern of 0.2 μm as shown in FIG. 3 was formed on the formed titanium oxide base film by using a photolithography technique.

0.1 mol / l was added to 50 g of ethyl silicate ("Ethyl silicate 40" manufactured by Colcoat).
(0.1N) 9g of hydrochloric acid and ethyl cellosolve (EC) 4
4 g was added, and the mixture was stirred at room temperature for 2 hours to prepare a coating solution.
Then, as shown in Table 1, after adding 7.3 g of ethyl cellosolve to 2.5 g of the coating solution, 0.2 g of chloroauric acid was added.
This was added to prepare a metal dispersion film raw material coating liquid 1. The metal dispersion film raw material coating solutions 2 and 3 used in Examples 2 and 3 were also prepared and prepared in the amounts shown in Table 1.

Next, a metal dispersion film raw material coating solution was coated on the patterned titanium oxide base film at a rotational speed of 1500 m.
Spin coated at in ^-1 . After air-drying, heat treatment was performed at 250 ° C. for 2 hours to deposit gold fine particles at the interface of the titanium oxide film, followed by baking at 580 ° C. for 30 minutes.

Tables 2 and 3 show the mass% of each composition when the oxide was formed. When the structure of the obtained glass substrate was observed by a transmission electron microscope (hereinafter abbreviated as TEM), it was confirmed that gold (Au) was segregated at the film interface between titanium oxide and silicon oxide. .

When the obtained glass substrate is irradiated with light perpendicular to the reference plane as shown in FIG. 3, absorption of a polarized light component (S-polarized light component) in a direction in which metal fine particles are arranged with respect to incident light having a wavelength of 900 nm. Was larger than the absorption of a polarized light component (P-polarized light component) perpendicular to the direction in which the metal fine particles were arranged, and as shown in Table 4, it was confirmed that a polarization characteristic with an extinction ratio of 53 dB at the maximum was developed.

The evaluation of the polarization characteristics used the extinction ratio defined by the following equation. The extinction ratio is determined by irradiating the sample with linearly polarized light, and the transmittance (Ts) when the major axis of the particle is parallel to the plane of polarization of the irradiated light.
%), And the transmittance (Tp%) when the major axis of the particle and the polarization plane of the irradiation light are perpendicular to each other was measured and calculated by the following equation.

Extinction ratio = ₁₀ Log ₁₀ (Tp / Ts) The adhesion was evaluated as acceptable when no peeling was observed when the film surface was wiped with a paper wiper. Table 1. Preparation Table of Metal Dispersion Film Raw Material Coating Solution =============================== Example Silicon Oxide Raw Material Chloroauric Acid EC ―――――――――――――――――――――――――――――――― 1 2.5g 0.2g 7.3g 2 2.5g 0.056g 7 0.4g 3 2.5g 0.0053g 7.495g ===================================== Mass% of each composition when converted to an oxide (composition of base film) =========================== Example SiO ₂ TiO ₂ CeO ₂ ――――――――――――――――――――――――― 1-3 0% 100% 0% ============= ================ Table 3. Mass% of each composition when converted to an oxide (metal dispersion film) ======================= Example SiO ₂ Au ――――― ―――――――――――――――――― 184% 16% 2 95% 5% 3 99.5% 0.5% ============== ========== Table 4. Change in extinction ratio of incident light and change in characteristics when gold (Au) concentration is changed ============================= === Example Absorption Wavelength Extinction Ratio Transmission Loss Adhesion --------------------------------------------------------------------------- 1 900 nm 53 dB 0 0.4dB 2900nm 30dB 0.1dB 3900nm 10dB 0.3dB ====================================== (Example 4) Using a glass substrate as a substrate, 10 cm ×
A titanium oxide base film and a segregated gold (Au) -containing silicon oxide film are formed on a 10 cm glass substrate. A glass substrate was placed in a sputtering apparatus, and a target having a purity of 99.
A 99% titanium oxide target was used.

The sputtering is performed at a deposition rate of 2 nm / min.
To form a 200-nm-thick titanium oxide base film. The metal dispersion film raw material coating solution used in Example 1 was spin-coated on the titanium oxide base film at a rotation speed of 1500 min ^-1 . After air drying, heat treatment was performed at 250 ° C. for 2 hours to deposit gold fine particles at the titanium oxide film interface, and then firing was further performed at 580 ° C. for 30 minutes. These steps are
This was repeated twice to obtain a glass substrate on which a laminated body composed of alternating layers of a titanium oxide film and a silicon oxide film containing fine segregated gold (Au) particles was formed. The composition of the obtained glass substrate in the depth direction was analyzed by X-ray photoelectron spectroscopy.
Was segregated at the film interface between titanium oxide and silicon oxide.

When the obtained glass substrate is irradiated with light at an incident angle of 10 ° to 60 °, the absorption of the light component (S-polarized light component) in the direction parallel to the film surface direction becomes perpendicular to the film surface direction. It was larger than the absorption of the light component (P-polarized light component), and it was confirmed that polarization characteristics were exhibited. In addition, a wavelength of 610 nm
The shift of the absorption wavelength to the longer wavelength side by changing the incident angle of light with respect to the incident light of ~ 800 nm reflects that the apparent aspect ratio of the fine gold particles is increased. Conceivable.

The incident angle is defined as a plane parallel to the substrate as a reference plane, and an angle at which light passes through the reference plane is defined as an incident angle. Table 5. Change in absorption wavelength of wavefront of light parallel to film surface when incident angle is changed and characteristic table ========================== ==== Working Example Incident Angle Absorption Wavelength Extinction Ratio Transmission Loss Adhesion ――――――――――――――――――――――――――――――― 610 nm 12 dB 0.1 dB ○ 4 45 ° 650 nm 14 dB 0.2 dB ○ 4 30 ° 730 nm 11 dB 0.4 dB ○ 4 10 ° 800 nm 13 dB 0.1 dB ○ ===================== ============== (Examples 5 to 8) 0.1 mol / to 50 g of ethyl silicate ("Ethyl silicate 40" manufactured by Colcoat)
l (0.1N) hydrochloric acid 6g and ethyl cellosolve (EC)
Was added and stirred at room temperature for 2 hours to prepare a silicon oxide stock solution. The silicon oxide solid content is 20 with respect to the silicon oxide stock solution.
% By mass.

Next, 2 mol of acetylacetone was added dropwise to 1 mol of the stirred titanium isopropoxide with a dropping funnel to prepare a titanium oxide stock solution. The solid content of titanium oxide with respect to the titanium oxide stock solution is 16.5% by mass.

3 mol of acetylacetone was added to 1 mol of cerium nitrate hexahydrate, and the mixture was treated with stirring at 90 ° C. for 1 hour to prepare a cerium nitrate stock solution. The cerium oxide solid content relative to the cerium nitrate stock solution was 23.2% by mass.

As shown in Tables 6 and 7, base material coating solutions 5 to 8 were prepared from the respective stock solutions prepared as described above. Table 6 shows the prepared amount of each raw material liquid, and Table 7 shows the mass% when the raw material was converted to an oxide. Table 6. Preparation amount of base film raw material coating liquid =================================== Example Silicon oxide raw material Oxidation Titanium raw material Cerium oxide raw material EC ―――――――――――――――――――――――――――――――――― 5 0.99g 1.59g 1 0.68 g 5.74 g 6 2.02 g 1.09 g 1.15 g 5.74 g 7 2.56 g 0.82 g 0.87 g 5.75 g 8 2.89 g 0.66 g 0.70 g 5.75 g ====== ============================= % By mass of each composition when converted to an oxide (composition of base film) ============================= SiO ₂ TiO ₂ CeO ₂ ―――――――――――――――――――――――――――――― 5 23.2% 30.8% 46.0% 6 47.5% 21.1% 31.4% 7 60.2% 16.0% 23.8% 8 67.9% 12.9% 19.2% ============ =========================
Gravure coating was performed to a thickness of μm. After air drying, heat-treat at 250 ° C for 2 hours, and further heat at 500 ° C for 3 hours.
Baking was performed for 0 minutes to form a base film. A pattern of 0.20 μm line & space as shown in FIG. 3 was formed on the formed base film by using a photolithography technique.

Next, the metal dispersion film raw material coating solution used in Example 1 was spin-coated on the pattern-formed base film at a rotation speed of 1500 min ^-1 . After air drying,
After heat treatment at 250 ° C. for 2 hours to deposit gold fine particles at the interface of the underlayer, firing was further performed at 580 ° C. for 30 minutes.

When the obtained glass substrate is irradiated with light perpendicular to the reference plane as shown in FIG.
The absorption of the polarized light component in the direction in which the metal fine particles are aligned with respect to the incident light of from 1500 nm is greater than the absorption of the polarized light component perpendicular to the direction in which the metal fine particles are aligned, and the extinction ratio exhibits a polarization characteristic of up to 48 dB. It was confirmed that. Table 8 shows the polarization characteristics. Table 8. Polarization Characteristics Table ================================== Example Absorption Wavelength Extinction Ratio Transmission Loss Adhesion- ―――――――――――――――――――――――――――――――― 5 1500nm 48dB 0.3dB ○ 6 1300nm 43dB 0.4dB ○ 7 1200nm 45 dB 0.3 dB 8 1000 nm 42 dB 0.2 dB ==================================== SiO of Base Film _{As the two} components increase, the absorption wavelength shifts to the shorter wavelength side because the particle diameter of the metal fine particles deposited at the interface with the base film becomes smaller, and the ratio between the direction parallel to the particle deposition surface and the thickness direction (aspect ratio) Ratio) becomes smaller.

These results suggest that by changing the composition of the underlayer, the aspect ratio of the fine particles deposited on the underlayer interface can be controlled, and that the polarization performance in a wide range can be exhibited. Indicates that it can be done. (Examples 9 to 11) On the patterned titanium oxide base film used in Example 1, a metal dispersion film raw material coating solution prepared as shown in Table 9 was spin-coated at a rotational speed of 1500 min ^-1. did.

As a raw material of zirconium oxide, 28.7 g of ethyl acetyl acetate was added to 38.7 g of tetrabutoxyzirconium, and the mixture was stirred for 2 hours to prepare a zirconium stock solution. The zirconium oxide solid content based on the zirconium stock solution is 19.0% by mass.

The applied coating liquid of the metal dispersion film material was air-dried, and then heat-treated at 250 ° C. for 2 hours to deposit gold fine particles at the interface of the underlayer, and further baked at 580 ° C. for 30 minutes. T
The structure of the obtained glass substrate was observed by EM, and it was confirmed that gold (Au) was segregated at the film interface between the titanium oxide base film and the silicon oxide / zirconium oxide film.

When the obtained glass substrate is irradiated with light perpendicular to the reference plane as shown in FIG.
It was confirmed that a polarization characteristic with a maximum extinction ratio of 55 dB was developed for incident light of 750 nm. Table 11 shows the polarization characteristics. Table 9. Preparation amount of metal dispersion film raw material coating liquid =================================== Example Silicon oxide raw material Zirconium oxide raw material EC chloroauric acid ―――――――――――――――――――――――――――――――――― 9 2.25g 0.26g 0.2g 7.3g 10 1.25g 1.31g 0.2g 7.2g 11 0.75g 1.83g 0.2g 7.2g ================== ================== % By mass of each composition when converted to an oxide (composition of metal dispersion film) =========================== Example SiO ₂ ZrO ₂ Au ―――――――――――――――――――――――――― 9 75.6% 8.4% 16.0% 10 42.0% 42.0% 16.0% 11 8.4% 75.6% 16.0% =========================== Table 11. Polarization Characteristics Table =============================== Example Absorption Wavelength Extinction Ratio Transmission Loss Adhesion ―――――― ――――――――――――――――――――――――― 9 850nm 43dB 0.4dB ○ 10 800nm 45dB 0.3dB ○ 11 750nm 55dB 0.2dB ○ ==== =========================== The above results show the ability to deposit metal fine particles of zirconium oxide on the interface of the underlayer and the ability of silicon oxide The difference with the ability to precipitate metal fine particles at the interface of the underlayer is clarified,
Specifically, zirconium oxide, compared to silicon oxide,
This indicates that there is a tendency to reduce the particle size of the metal fine particles deposited at the interface of the base film. That is, as the content of zirconium oxide increases, the absorption wavelength shifts to the shorter wavelength side, because the size of the fine metal particles deposited at the interface of the base film becomes smaller, thereby reducing the apparent aspect ratio. It is considered something. This indicates that the aspect ratio of the precipitated metal fine particles can be controlled by adjusting the amount of zirconium oxide.

Example 12 A glass substrate was used as a substrate, and a titanium oxide film and a segregated silver (Ag) -containing silicon oxide film were formed on a glass substrate of 10 cm × 10 cm.

In the same manner as in Example 1, a 0.20 μm line & space pattern was formed to form a titanium oxide base film. To 50 g of ethyl silicate (“Ethyl silicate 40” manufactured by Colcoat), 0.1 mol /
l (0.1N) 9g nitric acid and ethyl cellosolve (EC)
44 g was added and the mixture was stirred at room temperature for 2 hours to prepare a coating solution. Then, 6.5 g of ethyl cellosolve was added to 2.5 g of the coating solution, and then 1.0 g of an ethylene glycol solution containing 20% by mass of silver nitrate was added to prepare a metal dispersion film raw material coating solution.

Next, a metal dispersion film raw material coating solution was coated on the patterned titanium oxide base film at a rotational speed of 1500.
Spin coated at min ^-1 . After air drying, USHI
Using an O company ultraviolet (UV) irradiator, the center wavelength is 36
5 nm, UV intensity on the irradiated surface is 10 mW / cm
^By irradiating the ultraviolet light of No. ² for about 30 seconds, silver (Ag) fine particles were deposited on the interface of the titanium oxide base film.

After irradiation with ultraviolet light, a heat treatment was performed at 300 ° C. for 20 minutes. When the structure of the obtained glass substrate was observed by TEM, it was confirmed that silver (Ag) was segregated at the film interface between the titanium oxide base film and the silicon oxide film.

When the obtained glass substrate is irradiated with light perpendicular to the reference plane as shown in FIG. 3, the absorption of the polarization component in the direction in which the metal fine particles are aligned with the incident light having a wavelength of 800 nm is reduced. It becomes larger than the absorption of the polarized light component perpendicular to the direction in which are arranged, and it was confirmed that a polarization characteristic with an extinction ratio of 51 dB was developed.

Table 12 shows the composition of the metal dispersion film, and Table 13 shows the polarization characteristics. Table 12. Mass% of each composition when converted to an oxide (metal dispersion film) ===================== Example SiO ₂ Ag ――――――― ―――――――――――――― 12 80.6% 19.4% ===================== Polarization Characteristics Table =============================== Example Absorption Wavelength Extinction Ratio Transmission Loss Adhesion ―――――― ――――――――――――――――――――――――― 12 800nm 51dB 0.2dB ○ ================== ============= The above results show that, similarly to gold, polarization characteristics are exhibited by selectively depositing silver fine particles at the interface of the underlayer film, similarly to gold. I have. Similarly to gold, it can be easily imagined that the polarization characteristics can be controlled by changing the composition of the base film or the composition of the metal dispersion film raw material coating solution.

Further, as a means for decomposing and reducing the metal raw material from the coating liquid for the metal dispersed film raw material and segregating the metal fine particles at the interface of the base film, a means for irradiating electromagnetic waves such as ultraviolet rays may be effectively used in addition to the means by heating. This example shows that it can be used. (Example 13) Bismuth nitrate stock solution was prepared by dissolving 10 g of bismuth nitrate with 19.0 g of acetylacetone.
The bismuth oxide solid content relative to the bismuth nitrate stock solution was 25.
It becomes 2% by mass.

The above bismuth nitrate stock solution (16.9 g) was mixed with the titanium oxide stock solution (6.5 g) used in Examples 5 to 8,
Ethyl cellosolve (76.5 g) was added to prepare a base film raw material coating solution.

A gravure coating was carried out on a glass substrate with the above-mentioned base film raw material coating solution so that the film thickness became 1/6 μm. After air drying, heating and drying were performed at 250 ° C. The gravure coating and the heat drying were performed as one set of processing, and this processing was repeated six times in total, so that the film thickness became 1 μm. Further, baking was performed at 500 ° C. for 30 minutes to form a base film composed of titanium oxide and bismuth oxide.

A line and space pattern of 0.2 μm as shown in FIG. 3 was formed on the formed base film by photolithography. Next, the metal dispersion film raw material coating solution used in Example 1 was spin-coated on the pattern-formed base film at a rotation speed of 1500 min ^-1 . After air drying, heat treatment was performed at 250 ° C. for 2 hours to deposit gold fine particles at the interface of the underlayer.
Baking was performed at 0 ° C. for 30 minutes.

When the obtained glass substrate is irradiated with light perpendicular to the reference plane as shown in FIG. 3, the absorption of the polarization component in the direction in which the metal fine particles are arranged with respect to the incident light having a wavelength of 630 nm is arranged. It became larger than the absorption of the polarization component perpendicular to the direction, and it was confirmed that a polarization characteristic with an extinction ratio of 45 dB was developed. Table 14 shows the composition of the underlayer and Table 1
5 shows the polarization characteristics. Table 14. % By mass of each composition of the base film when converted to an oxide ====================== Example TiO ₂ Bi ₂ O ₅ ――――― ――――――――――――――――― 13 15% 85% ====================== Polarization Characteristics Table ============================ Example Absorption Wavelength Extinction Ratio Transmission Loss Adhesion ―――――――― ――――――――――――――――――――― 13 630nm 45dB 0.1dB ○ ======================= ======= (Example 14) Using a glass substrate as a substrate, 10 cm
A tin oxide base film and a segregated gold (Au) -containing silicon oxide film are formed on a glass substrate of × 10 cm. Glass substrate CV
D (Chemical vapor deposition) apparatus, and a tin oxide film having a thickness of 2 μm was formed using monobutyltin trichloride as a raw material.

A 0.5 μm line & space pattern as shown in FIG. 3 was formed on the formed tin oxide film by using a lift-off technique. Next, the metal dispersion film material coating solution used in Example 1 was spin-coated on the tin oxide base film on which the pattern was formed at a rotation speed of 1500 min ^-1 . After air-drying, heat treatment was performed at 250 ° C. for 2 hours to deposit gold fine particles at the interface of the underlayer, followed by baking at 580 ° C. for 30 minutes.

When the obtained glass substrate is irradiated with light perpendicularly to the reference plane as shown in FIG. 3, the absorption of the polarized light component in the direction in which the metal fine particles are arranged with respect to the incident light having a wavelength of 800 nm is arranged. It became larger than the absorption of the polarization component perpendicular to the direction, and it was confirmed that the polarization characteristic with an extinction ratio of 55 dB was developed. Table 16 shows the polarization characteristics. Table 16. Polarization characteristics table ============================== Example Absorption wavelength Extinction ratio Transmission loss Adhesion ---- ――――――――――――――――――――――― 14 800nm 55dB 0.1dB ○ ==================== ========== (Comparative Example 1) Using a glass substrate as a substrate, 10 cm ×
A silicon oxide base film and segregated gold (A
u) containing silicon oxide film layer. A glass substrate was placed in a sputtering apparatus, and a target having a purity of 99.
A 99% silicon oxide target was used. In the sputtering, a silicon oxide film having a thickness of 1 μm was formed at a deposition rate of 40 nm / min.

The formed silicon oxide base film is formed by photolithography using a photolithography technique as shown in FIG.
A line and space pattern of μm was formed. Next, the metal dispersion film raw material coating solution used in Example 1 was rotated at 1500 mi on the patterned silicon oxide base film.
Spin-coated at n- ¹ . After air drying, 2 at 250 ° C
After heat treatment for hours, the gold (Au) fine particles did not segregate at the film interface.

When the structure of the obtained glass substrate was observed by TEM, it was confirmed that gold was uniformly dispersed in the depth direction in the metal dispersion film. Even when the obtained glass substrate was irradiated with light perpendicular to the reference plane as shown in FIG. 3, clear polarization characteristics could not be confirmed. Table 1
8 shows the polarization characteristics. (Comparative Example 2) A glass substrate is used as a substrate. Example 5
After adding 0.06 g of the titanium oxide stock solution to 2.45 g of the silicon oxide stock solution used in Nos. 8 to 8, ethyl cellosolve was added to 7.4.
9 g was added to prepare a base film raw material coating solution.

On a glass substrate, the base film raw material coating solution was
Gravure coating was performed to a film thickness of 1 μm. After air drying, heat-treat at 250 ° C for 2 hours, and further heat at 500 ° C for 3 hours.
Baking was performed for 0 minutes to form a base film.

A pattern of 0.2 μm line & space as shown in FIG. 3 was formed on the formed base film by using a photolithography technique. Next, the metal dispersion film raw material coating solution used in Example 1 was spin-coated on the pattern-formed base film at a rotation speed of 1500 min ^-1 . After air drying and heat treatment at 250 ° C. for 2 hours, the gold (Au) fine particles did not segregate at the film interface and the color was pink.

When the structure of the obtained glass substrate was observed by TEM, it was confirmed that gold was uniformly dispersed in the metal dispersion film in the depth direction. Table 17 shows a composition table (in terms of oxide) of the base film.

Even when the obtained glass substrate was irradiated with light perpendicular to the reference plane as shown in FIG. 3, no clear polarization characteristics could be confirmed. Table 18 shows the polarization characteristics. Table 17. % By mass of each composition when the base film was turned into an oxide (composition of base film) ====================== Comparative Example SiO ₂ TiO ₂ ――――――――――――――――――――――― 1 100% 0% 2 98.05% 1.95% ============= ========== Polarization characteristics table ============================== Comparative example Absorption wavelength Extinction ratio Transmission loss Adhesion ---- ――――――――――――――――――――――― 1 550nm 0.8dB 0.1dB ○ 2 560nm 0.9dB 0.3dB ○ ========= ===================== These results, or even the underlying film only of silicon oxide, titanium oxide content is less than 2 mass% in terms of TiO ₂ In this case, the metal fine particles are not selectively deposited on the interface of the underlayer. Therefore, in order to selectively deposit the metal particles on the interface of the underlayer, at least the content of titanium oxide must be reduced to TiO _2. At 2% by mass or more was confirmed. (Comparative Examples 3 and 4) Using a glass substrate as a substrate, 10c
A titanium oxide base film and a segregated gold (Au) -containing silicon oxide film are formed on a glass substrate of mx 10 cm. A glass substrate is placed in a sputtering apparatus, and a target having a purity of 9
A 9.99% titanium oxide target was used. In the sputtering, a titanium oxide film having a thickness of 1 μm was formed at a deposition rate of 40 nm / min.

A 0.2 μm line & space pattern as shown in FIG. 3 was formed on the formed base film by using a photolithography technique. As the coating liquid for the metal dispersion film, a raw material coating liquid as shown in Table 19 was prepared. Next, a metal dispersion film raw material coating solution was spin-coated on the patterned base film at a rotation speed of 1500 min ^-1 . After air drying, heat treatment was performed at 250 ° C. for 2 hours.

Table 20 shows a composition table (in terms of oxide) of the metal dispersion film. When the obtained glass substrate was irradiated with light perpendicular to the reference plane as shown in FIG. 3, in Comparative Example 3, clear plasmon absorption could not be observed.

In Comparative Example 4, the condensation polymer of the silicon oxide raw material was separated from the substrate when gold particles precipitated at the interface of the underlying film due to the heat treatment, and a uniform film could not be formed. Table 21 shows the polarization characteristics.

From the above results, if the concentration of gold (Au) is too low, the size of the fine metal particles deposited at the interface of the underlayer becomes small, so that sufficient polarization characteristics are not exhibited, and
u) It was confirmed that even if the concentration was too high, the adhesion to the underlying film was lowered, and it was impossible to form a uniform film. Table 19. Preparation amount of metal dispersion film raw material coating liquid =========================== Comparative Example Silicon oxide raw material EC chloroauric acid ―――――――――――――――――――――――― 3 2.5g 0.0020g 7.5g 4 2.5g 1.10g 6.4g ======= ====================== Mass% of each composition when converted to an oxide (metal dispersed film) =========================== Comparative Example SiO ₂ Au- ―――――――――――――――――――――――――― 3 99.81% 0.19% 4 49.3% 50.7% ====== ===================== Polarization characteristics table ============================== Comparative example Absorption wavelength Extinction ratio Transmission loss Adhesion ---- ――――――――――――――――――――――― 3 ― 0.001dB 0.002dB ○ 4 ― Not evaluated Not evaluated × =========== ===================

[0091]

As described above, according to the present invention, a base film containing a base film raw material compound group A and / or B as a main component is formed on a transparent substrate, and a metal compound is formed on the base film. After forming a metal dispersion film by applying a coating solution containing, as a main component, a compound of at least one element selected from a metal dispersion film coating liquid raw material group, and then performing a heat treatment or electromagnetic wave irradiation, the base film and Fine metal particles can be selectively deposited at the film interface with the metal dispersion film, whereby an element having polarization characteristics can be obtained.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a method for manufacturing a polarizing element.

FIG. 2 is a simplified diagram showing a state of metal fine particles deposited at a film interface between a base film and a metal dispersion film.

FIG. 3 is a simplified diagram showing a polarizing element according to the first embodiment.

FIG. 4 is a simplified diagram showing a polarizing element according to a second embodiment.

FIG. 5 is a simplified diagram showing a polarizing element according to a third embodiment.

FIG. 6 is a simplified diagram showing a polarizing element according to a fourth embodiment.

[Explanation of symbols]

11: glass substrate, 11a: reference plane, 12: base film, 1
3 ... metal dispersion film, 14 ... metal fine particles, 15 ... increase reflection film,
16 ... Film interface.

Claims (6)

[Claims] An undercoating film containing a component having an action of attracting metal fine particles is formed on a transparent substrate, and a coating solution containing metal ions is applied on the undercoating film to form a metal dispersion film. Then, a method of manufacturing a polarizing element, comprising selectively depositing metal fine particles at a film interface between the undercoat film and the metal dispersion film. 2. On a transparent substrate, titanium oxide, cerium oxide, tin oxide, bismuth oxide, cobalt oxide, copper oxide,
Aluminum oxide, magnesium oxide, manganese oxide,
Chromium oxide, indium oxide, vanadium oxide, iron oxide, nickel oxide, zinc oxide, tungsten oxide, tantalum oxide, hafnium oxide, barium oxide, ytterbium oxide, niobium oxide, molybdenum oxide, yttrium oxide, ruthenium oxide, germanium oxide, lead oxide A base film containing at least one compound selected from the group consisting of boron oxide as a main component, and a metal compound, silicon, zirconium, titanium, cerium, tin, bismuth, cobalt, Copper, aluminum, magnesium, manganese, chromium, indium, vanadium, iron, nickel, zinc, tungsten, tantalum, hafnium, barium, ytterbium, niobium,
After forming a metal dispersion film by applying a coating solution containing at least one compound selected from the group consisting of molybdenum, yttrium, ruthenium, germanium, lead, and boron as a main component, forming a metal dispersion film, and then performing heat treatment or electromagnetic wave irradiation. Wherein a fine metal particle is selectively deposited at a film interface between the undercoat film and the metal dispersion film. 3. The method according to claim 1, wherein the underlayer contains at least one compound selected from the group consisting of silicon oxide and zirconium oxide. 4. The base film, expressed in mass%, is titanium oxide, cerium oxide, tin oxide, bismuth oxide, cobalt oxide, copper oxide, aluminum oxide, magnesium oxide, manganese oxide, chromium oxide, indium oxide, or oxide. From the group consisting of vanadium, iron oxide, nickel oxide, zinc oxide, tungsten oxide, tantalum oxide, hafnium oxide, barium oxide, ytterbium oxide, niobium oxide, molybdenum oxide, yttrium oxide, ruthenium oxide, germanium oxide, lead oxide, and boron oxide 2 to 100% by mass of at least one selected compound, silicon oxide,
The method for producing a polarizing element according to any one of claims 1 to 3, further comprising 0 to 98% by mass or less of at least one compound selected from the group consisting of zirconium oxide. 5. The coating liquid as a raw material of the metal dispersion film,
In terms of mass% when solidified, the metal is 0.2 to 0.2%.
50% by mass, silicon oxide, zirconium oxide, titanium oxide, cerium oxide, tin oxide, bismuth oxide, cobalt oxide, copper oxide, aluminum oxide, magnesium oxide,
Manganese oxide, chromium oxide, indium oxide, vanadium oxide, iron oxide, nickel oxide, zinc oxide, tungsten oxide, tantalum oxide, hafnium oxide, barium oxide, ytterbium oxide, niobium oxide, molybdenum oxide, yttrium oxide, ruthenium oxide, germanium oxide 5. The method for producing a polarizing element according to claim 1, comprising 50 to 99.8% by mass of at least one compound selected from the group consisting of lead oxide and boron oxide. . 6. A polarizing element manufactured by the manufacturing method according to claim 1. Description: